Catalytic oxidation of ketols



wherein the loose bonds-may be taken up by to the carbonyl group and the grouping will ,isopropyl ketol Patented June 9, 1936 UNITED STATES PATENT OFFICE 2,043,950 CATALYTIC OXIDATION OF KETOLS Martin de Sim and Sumner H. McAllister,

Berkeley,' Calif assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application September 22, 1934,

Serial No. 745,106

18 Claims. (Cl. 260--134) This invention relates to the catalytic oxidation of'ketone alcohols and is more particularly concerned with reacting primary and/or sec-- ondary 'ketone alcohols withoxygen in the preshydrogen, alkyl, alkoxy, carboxylic, heterocyclic, aralkyl, aryloxy and/or aralkoxy groups which may or may not be further substituted, and may or may not contain unsaturated bonds. The loose bonds, other than that'on' the carbinol group may be further taken up by-,OH and/or =0 radicals. "n in such a characteristic groupings may-be zero or an integer. When n is zero the carbinol groupwill be directly attached come I I I? F g I I Typical ketols which may be used in our process are, for example, acetol if our-04111203 and its homologues such as ethyl ketol Calls--GHaOH propyl ketol (CHahCH--CHaOH andthe like, or their, isomers such as dimethyl ketol CHrC-CHOH-OH:

methyl ethyl ketol and the like. Other contemplated ketols are p-aceto ethyl alcohol CHs--OHn-OHaOH -y--aceto propyl alcohol H CHr-C-CHr-CHr-CHgOH and their homologues." Examples of suitable polyhydric ketols are dihydroxy acetone -noH=o ioH.oH

a, 'y dihydroxy methyl ethyl ketone o nomc--onon-om and the like; while polyketonic ketols include hydroxy .acetylacetone o omtiom-t':omon diacetyl carbinol 0 0 om-E-cnon--om hydroxy diacetyl 4 o o onri-omon and the like.

above exemplified, the aryl and aralkyl derivatives such as benzyl ketol benzyl dimethyl ketol o I I Oom-om-Awnon-om phenyl dihydroxy acetone 0 ll O-onon-o-omon Instead of the alkyl compounds may occur to a greater or lesser degree vention is as follows: The

benzoyl methyl ketol if t Qo-onon-c-om benzoyl carbinol phenyl-acetyl-carbinol O t CHOH CH;

derstood as distinguishing our process from dehydrogenation processes which comprise splitting hydrogen atoms from a hydrogen-containing compound whereby molecularhydrogen is obtained as a reaction product. In an oxidation process, as herein defined, the ketol reacts with oxygen forming water and a new carbonyl group. The chief product of our process is thus usually a polycarbonylic compound, although in certain cases a rupture of the molecule with the formation of simpler monocarbonylic compounds, usually acids.

Our invention may be applied in many ways. The oxidation may, for example, be effected in either the liquid, liquid-vapor or the vapor phase. One convenient method of carrying out our inketol to be oxidized is distilled in a stream of oxygen, or free oxygencontaining gas, into a column packed with the desired catalyst. At the top of the column a reflux may be maintained to return substantially all the unchanged ketol to the reaction zone while allowing the more volatile oxidized prodnot to escape and be separately collected. In this method of procedure the oxidation is efiected at, or below, the boiling point of the ketol.

As a result the reaction, in certain cases, may

be relatively slow and comparatively long times of contact may be required for its completion. This may, in some cases, lead to the formation of some higher oxidation products and other side reactions to a certain extent.

An alternative method of procedure in applying our invention comprises effecting the ketol oxidation entirely in the vapor phase. For example, the ketol vapors may be passed in admixture with a definite ratio of air and/or oxygen over an appropriate catalyst heated to the reaction temperature. The exit vapors may be passed into a fractionating column wherein the desired oxidized product is separated and the unreacted ketol recycled through the oxidation zone. The water formed as a lay-product of the oxidation reaction may be separated from the product and/ or unreacted ketol by any suitable method. In many instances, the neutralized or originally employed ketol need not be free of water.

'gold, gold-silver alloy,

,In this method of operation higher temperatures may be used than in the previously described modification and consequently shorter times of contact are permissible. The practical upper limit of reaction temperature is set, however, by the stability, especially toward pyrolytic decomposition, of the ketol being oxidized as well as of the oxidation product sought, at the existing pressure. The use of temperatures below about 200 C. has been found, in the majority of cases, to be impractical, due to the low rate of oxidation unless impractically long times of contact are provided. We preferably employ therefore, in vapor phase operation temperatures between about 200 C. and about 500 C.

The reaction temperature may be controlled in any convenient manner. As the reaction in our process is predominantly exothermic, means for absorbing heat are usually required; diluent gases admixed with the oxygen may serve this purpose or an inert substance of suitable constant boiling point may be introduced, or resort may be had to other well known methods of control.

Either superatmospheric, atmospheric or subatmospheric pressure may be used. Superatmospheric pressures favor the oxidation reaction but in some cases subatmospheric pressures are advisable in order to avoid decomposition of the ketol. An intermittent, batch or continuous mode of operation may be employed.

In any method of operation the ratio of free oxygen to ketol present in the reaction zone has a marked effect on the course of the reaction. Excess oxygen tends to increase the rate of conversion of the ketol and also promotes the formation of highly oxidized products such as acids and acid anhydrides for example. Where less highly oxidized products, such as diketones and/or ketone aldehydes, are desired, it is preferable, therefore, to carry out our invention with equivalent, or less than equivalent, oxygen ratios.

The catalyst chosen for carrying out the reaction also markedly influences the results obtained. Among the suitable catalysts which may be employed in the solid state, the following may be mentioned as examples: copper oxide, copper, brass, silver, silver-zinc and silver arsenic alloys,

platinum, palladium, cobalt, cobalt oxide, nickel, and nickel oxides, vanadium, vanadyl sulfate, silver vanadate, aluminum, cadmium, chromium, chromium oxide, tin, stannous oxide, tungsten, manganous oxide, zinc, zinc oxide, zinc sulfide, etc. Particularly suitable are the elements of the third period of the Periodic Table such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and selenium and compounds and mixtures thereof. The most desirable catalyst, in any case, is one which possesses a moderate initial actvity and is substantially devoid of the tendency to induce undesirable side reactions such as dehydration, condensation, polymerization, and the like, and possesses a freedom from deterioration as a result of sintering or poisoning. We

have found activated copper, copper oxide, and

silver to .be particularly suitable catalysts for our process.

The particular catalyst chosen may be activated in a variety of well known ways. For example,

active metal catalysts may be prepared by either I other catalystic metals or compounds or with 75 be understood, that many other applications and modifications are possible without departing from the spirit thereof.

Example I Dimethyl ketol was distilled under good reflux, in a stream of oxygen, through a column packedwith 6110. The reflux of the column was so regulated that the unchanged ketol was returned to the still and at the top of the column only a mixture of substantially pure diacetyl and water was taken off. Excess oxygen over that required for formation of diacetyl was avoided throughout the operation.

After about 60% of the still charge had passed over, the collected product was found to consist of Percent Diacetyl 69 Ketol 4 Water 27 The still bottoms representing about 40% of the original charge werefound to be of the following approximate composition:

Percent Dimethyl ketol about 25 Acetic acid and acetic anhydride about 50 Ketol acetate and condensations products about 25 The crude diacetyl on fractionation gave a yield of 48% of the pure product based on the dimethyl ketol consumed.

Example II Dimethyl ketol and air in a definite ratio were Reaction Oxygen Ketol Yield of tempera- (percent of reacted diacetyl ture C. theory) percent (percent of Y theory) The diacetyl obtained by rectification of the reaction product was in every case exceptionally pure. By recycling the unreacted dimethyl ketol complete conversion was ultimately attained in all cases. It was found to be' unnecessary to remove the water formed in the reaction before recycling the unreacted ketol.

It is thus evident that our process provides a commercially available method for producing a wide variety of valuable products, particularly diketones and ketone aldehydes. The diketones are especially useful products, diacetyl, for example, being widely applied as a carrier of the aroma of butter, vinegar, coffee, honey and the like; while other diketones, as well, serve as important intermediates in the synthesis of valuable cyclic compounds. They are valuable starting materials for the preparation of synthetic resins and plastics.

Our process for the preparation of these products offers many advantages over previous meth ods involving other starting materials, particularly by providing for selective oxidation at the carbinol group or groups which eliminates undesirable oxidation at other parts of the molecule and gives economical yields.

While we have in the foregoing described in some detail the preferred embodiment of our invention and some variants thereof, it will be understood that this is only for the purpose of making the invention more clear and that the invention is not to be regarded as limited to the details of operation described, nor is it dependent upon the soundness or accuracy of the theories which we have advanced as to the advantageous results attained. On the other hand, the invention is to be regarded as limited only by the terms of the claims, in which it is' our intention to claim all novelty inherent therein as broadly as is possible in view of the prior art.

We claim as our invention:

1. A processfor the oxidation of a ketol of the class which consists of primary and secondary ketone alcohols, to a compound containing a car- 3 bonyl group in place of a carbinol group, which comprises reacting said ketol with free oxygen in the presence of a solid oxidizing catalyst.

2. A processfor the oxidation of a ketol containing a. carbonyl group at least once removed wherein R and R are members of the group consisting of hydrogen, alkyl, allfoxy, carboxylic, heterocyclic, aralkyl, aryloxy and aralkoxy groups, to a compound containing an oxalyl group-which comprises reacting said ketol with free oxygen in the presence of a solid oxidizing catalyst.

4. A process for the oxidation of a mono carbonylic ketol, other than a tertiary carbinol, to a polycarbonylic compound, which comprises reacting said ketol with free oxygen in the presence of a solid oxidizing catalyst. I

5. A process for the oxidation of aprimary ketol to a compound containing a carbonyl group in the place of the primary carbinol group, which comprises reacting said ketol with free oxygen in the presence of an oxidizing catalyst.

6. A process for the oxidation of a secondary ketol to a compound containing a carbonyl group other than a tertiary carbinol, to an alkyl compound containing a carbonyl group in place or a carbinol group, which comprises reacting said alkyl ketol with tree oxygen in the presence of a solid oxidizing catalyst.

B. A process for the oxidation of dimethyl ketol to diacetyl which comprises reacting dimethyl ketol with free oxygen in the presence of a solid oxidizing catalyst.

9. A process for the oxidation of ethyl ketol to ethyl glyoxal which comprises reacting'ethyl ketol with free oxygen in the presence 0! an oxidizing catalyst.

10. A process for the oxidation of a ketol containing cyclic nuclei to a compound containing other than a tertiary carbinolxto a compound containing a carbonyl group in place of a carbinol group, which comprises reacting said ketol with free oxygen in the presence of a catalyst containing an element of the third period 0! the periodic. table.

13. A process for the oxidation oi a lietol in accordance with claim 12 in which the catalyst contains copper.

14. A process for the oxidation or a ketol in accordance with claim 12 in which the catalyst is copper oxide.

15. A process for the oxidation of a ketol, other than a tertiary carbinol, to a compound containing a carbonyl group in place of a carbinol group, which comprises reacting said ketol in the vapor phase with free oxygen in the presence or an oxidizing catalyst.

16. A process for the oxidation of a ketol in accordance with claim 15 in which the reaction is carried out at a temperatureoi between about 200 C. and 500 C.

17. A process for the oxidation 01 a ketol, other than a tertiary carbinol, to a compound containing a carbonyl group in the place of a carbinol group which comprises reacting said ketol with free oxygen in the presence of an oxidizing catalyst at a temperature of about the boiling point of said ketol at the existing pressure.

18. A process for the oxidation of a ketol, other than a tertiary carbinol, to a compound containing a carbonyl group in place oi a carbinol group which comprises reacting said ketol with free gaseous oxygen in the presence of a solid oxidizing catalyst.

mm or: $1146. SUMNER H. McALLISTER. 

